Titanium‐Free <i>N</i>‐Sulfinyl Ketimine Formation by Transimination

Abstract Reaction of sulfinamides with in situ generated N ‐trifluoromethanesulfonyl ketimines occurs rapidly at room temperature in the presence of KO t ‐Bu. The precursor N ‐H imines are accessible by organolithium addition to nitriles or condensation of HMDS with ketones. This protocol avoids work‐up and reactor cleaning challenges encountered in the traditional Ti(OEt) 4 mediated condensation approach. The reaction works well for extremely hindered substrates, some of which were inaccessible with the Ti(OEt) 4 procedure.